CN117946741A

CN117946741A - Start-up method of hydrocracking device

Info

Publication number: CN117946741A
Application number: CN202211333908.5A
Authority: CN
Inventors: 翟维明; 刘锋; 晋超; 褚阳; 杨平; 杨清河
Original assignee: Sinopec Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Current assignee: Sinopec Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2022-10-28
Filing date: 2022-10-28
Publication date: 2024-04-30

Abstract

The invention relates to the technical field of catalyst startup, and discloses a startup method of a hydrocracking device, which comprises the following steps: (1) Filling a hydrocracking catalyst in a reaction bed layer of the hydrocracking device; (2) Introducing hydrogen into a reaction bed filled with a hydrocracking catalyst, heating the reaction bed to 100-140 ℃, then introducing diesel fraction and optionally vegetable oil to wet the reaction bed, and establishing closed circulation; (3) And (3) continuously heating the temperature of the reaction bed layer in the step (2) to 300-350 ℃, then switching raw oil, and continuously heating to the hydrocracking reaction temperature, wherein the hydrocracking catalyst is an ammonia passivation type sulfurized hydrocracking catalyst. The method has the advantages of simple starting process, safety, stability and environmental protection in the starting process, and effectively avoids the potential risk of injecting the vulcanizing agent and the passivating agent.

Description

Start-up method of hydrocracking device

Technical Field

The invention relates to the technical field of device startup, in particular to a startup method of a hydrocracking device.

Background

With the development of the global aviation industry and the increasing demand for clean fuels, the demand for clean aviation kerosene has been on the rise. The source of the clean aviation kerosene at present is that the index and performance of the hydrotreating of the straight-run aviation kerosene meet the aviation kerosene standard requirements, on the one hand, the heavy oil product is subjected to hydrocracking to break chains of macromolecular raw materials to obtain the aviation kerosene with a certain proportion meeting the requirements, and the processing amount of the straight-run aviation kerosene raw materials is difficult to realize rapid increase because the straight-run aviation kerosene is influenced by the processing amount of crude oil, so that the hydrocracking of the heavy oil to produce the aviation kerosene becomes an important method for meeting the market increasing demands of the aviation kerosene.

The active metal component of the hydrocracking catalyst has higher catalytic activity only when being converted into a vulcanized state, so that the catalyst is subjected to vulcanization treatment, which is important for fully playing the performance of the catalyst. At present, the sulfuration of hydrogenation catalysts is divided into three forms of in-device sulfuration, in-device activation of out-device sulfur carrier and out-device sulfuration. The in-reactor vulcanization is a vulcanization process of the catalyst in the reactor, a large amount of vulcanizing agent and carrier oil are needed, and meanwhile, waste gas and waste water generated in the vulcanization process pollute the environment; the external sulfur carrier internal activation is that the catalyst finishes the loading of sulfur-containing substances outside the device, active metals are not converted into a sulfur state, hydrogen is used for activating the catalyst after the catalyst is loaded into the reactor, high-concentration hydrogen sulfide gas can be generated in the process, and meanwhile, when the circulating gas is exhausted, a vulcanizing agent is still needed to be supplemented to maintain a certain hydrogen sulfide concentration, the operation process is relatively complex, and the risk of hydrogen sulfide leakage exists. The external vulcanization is a vulcanization mode which is advocated and promoted at present, the external vulcanization mode can be utilized to effectively save the time of starting work, ensure the safety of the starting work process and reduce the use of dangerous chemicals and leakage of high-concentration hydrogen sulfide.

After being vulcanized, the hydrocracking catalyst containing the molecular sieve has high hydrocracking activity, raw oil can undergo cracking reaction and hydrogenation reaction in the heating process, huge reaction heat is released, and the risk of 'flying temperature' of a catalyst bed exists, so that the hydrocracking catalyst needs to be passivated, the excessive initial activity of the hydrocracking catalyst is inhibited, and the safety of the catalyst, equipment and personnel is ensured. At present, nitrogen-containing compounds such as anhydrous liquid ammonia are injected during operation, namely a passivation method capable of effectively inhibiting the initial activity of a catalyst, but the anhydrous liquid ammonia is a pungent and toxic liquid, has the characteristic of inflammability and explosiveness, has certain danger when the anhydrous liquid ammonia is used industrially, causes great harm to the environment and human bodies if leakage occurs, and does not accord with the concepts of safety, health and environmental protection. Therefore, the molecular sieve passivation work of the hydrocracking catalyst is finished outside the reactor, and the high-cracking-activity molecular sieve is protected by utilizing certain alkaline substances, so that the steps in the starting stage can be effectively reduced, the risk of ammonia leakage is avoided, and the risk of 'flying temperature' in the starting stage is reduced. Patent application CN101492613a discloses a method for starting up a hydrocracking unit. The sulfur-carrying hydrocracking catalyst subjected to pre-vulcanization outside the reactor is used in the starting process, and anhydrous liquid ammonia is used for passivating the catalyst, so that a large amount of hydrogen sulfide gas and acid-containing sewage can be generated in the starting process, the risk of overtemperature caused by concentrated decomposition and heat release of sulfides is provided in the activation process, and meanwhile, the defects caused by ammonia injection in the prior art are overcome, so that certain hidden danger and harm are provided.

Patent application CN109777472a discloses a method for hydroprocessing. In the catalyst passivation stage, the pre-loaded nitride is used as a passivating agent to passivate the cracking agent, so that the aim of no need of using the passivating agent is fulfilled, but the catalyst is required to be vulcanized by continuously injecting a vulcanizing agent in the starting process, special vulcanizing equipment is required to be installed, and the problems of incomplete vulcanization, hydrogen sulfide leakage, long starting time, high cost and the like exist in the vulcanizing process.

Patent application CN103059969A discloses a method for passivating cracking agent by utilizing ammonia generated by reaction of high-nitrogen raw material and hydrogen as passivating agent in the starting process, thereby achieving the purpose of reducing the use of anhydrous liquid ammonia, and having the function of temporarily inhibiting cracking activity, but having complex operation, poor stability and difficulty in guaranteeing the passivation effect of molecular sieve, and simultaneously, the additional introduction of high-nitrogen raw material oil is likely to have new impurities introduced into a reaction system to influence the activity of a catalyst.

Patent application CN103566963a discloses a method of introducing basic nitrides onto a catalyst at a low temperature stage, then performing in-situ sulfiding and activation processes, while allowing a degree of control over the cracking reaction, introducing nitrides into sulfided catalysts in the form of aqueous solutions will have a significant impact on the hydrogenation activity of the catalyst, resulting in destruction of the active centers of the catalyst.

A method for producing jet fuel is disclosed in patent application CN 105419865A. By strictly controlling the composition in the raw materials, the saturation rate of the double-ring aromatic hydrocarbon is 70-90%, and the saturation rate of the single-ring aromatic hydrocarbon is 75-95%. The method adopts the catalytic cracking diesel oil as the raw material, has strict requirements on the raw material, and limits the practicability of the method.

Patent application CN103013559a discloses a hydrocracking process for selectively increasing aviation kerosene yield. In which it is involved to return the heavy diesel fraction (320-370 ℃) to the feedstock, to mix it with the feedstock, and to continue the subsequent hydrocracking reaction, which results in a decrease in the throughput of the plant, while the average energy and material consumption of the product is further increased.

Patent application CN107460003a discloses a method for increasing yield of aviation kerosene by hydrocracking. According to the method, the hydrocracking raw oil, the cyclic hydrocarbon raw material and the nitrogen-containing compound which can be selectively added are mixed to obtain mixed raw oil, and then the mixed raw oil is hydrocracked, so that the yield of aviation kerosene can be improved to a certain extent, but the raw material is complex in configuration, the source of the raw material needs to be accurately controlled, and the raw material adaptability is poor.

The distribution of different products in the hydrocracking process has great influence on the result, the good selectivity of the catalyst is beneficial to improving the yield of target products, the maximization of the yield and benefit of the target products is realized, and the improvement of the selectivity of the catalyst is significant through the adjustment and optimization of the process in the starting process.

Disclosure of Invention

The invention aims to solve the problems of long vulcanizing time, need of passivating agent and complex starting flow in the starting process of the hydrocracking device in the prior art, and provides a starting method of the hydrocracking device.

In order to achieve the above object, the present invention provides a startup method of a hydrocracking apparatus, wherein the method comprises:

(1) Filling a hydrocracking catalyst in a reaction bed layer of the hydrocracking device;

(2) Introducing hydrogen into a reaction bed filled with a hydrocracking catalyst, heating the reaction bed to 100-140 ℃, then introducing diesel fraction and optionally vegetable oil to wet the reaction bed, and establishing closed circulation;

(3) Continuously heating the temperature of the reaction bed layer in the step (2) to 300-350 ℃, then gradually changing raw oil into raw oil, and continuously heating to the hydrocracking reaction temperature;

The hydrocracking catalyst is an ammonia passivation type sulfuration hydrocracking catalyst.

Preferably, the nitrogen content of the diesel fraction is in the range of 0 to 900ppm, preferably 0 to 500ppm, more preferably 10 to 300ppm.

Preferably, the vegetable oil is selected from at least one of corn oil, soybean oil, peanut oil, rapeseed oil, coconut oil, sunflower seed oil, olive oil and cottonseed oil, and more preferably at least one of corn oil, soybean oil, peanut oil, rapeseed oil, coconut oil, sunflower seed oil and cottonseed oil.

Preferably, the vegetable oil has a distillation range of 180-540 ℃ and a bromine number of 10-25gBr/100mL.

Preferably, the diesel fraction is used in an amount of 100 to 2000 parts by weight and the vegetable oil is used in an amount of 0 to 300 parts by weight, compared to 100 parts by weight of the hydrocracking catalyst.

The method provided by the invention has the advantages that the starting time is short, the starting process is simple, the temperature can be directly increased to enable oil to start working, the stable production state is achieved in a short time, the time is saved by 2-4 days compared with the conventional starting process, the use of vulcanizing agents and the leakage of hydrogen sulfide are avoided, the flying temperature risk is reduced, a large amount of manpower and material resources are saved, the environmental pollution and the difficulty and the danger of operation are avoided, the investment in the starting process is reduced, and the method has certain economical and practical values.

The inventor of the invention finds in the study that the ammonia passivation type hydrocracking catalyst is matched with low-nitrogen diesel oil fraction and vegetable oil with a proper proportion to be used as starting oil, on one hand, the alkaline nitride is inevitably separated from the catalyst molecular sieve in the heating process to expose acid sites, the nitride in the low-nitrogen diesel oil is utilized to supplement and passivate the molecular sieve in the catalyst to ensure the stability of the heating process in the starting process, the occurrence of excessive cracking reaction is avoided, on the other hand, unsaturated hydrocarbon in the vegetable oil has higher polarity and can be preferentially adsorbed around the active sites of the catalyst, and long-chain unsaturated hydrocarbon with higher molecular weight is condensed in the heating process to form carbon precursor around the active sites, thereby effectively avoiding unordered growth of the active phase, improving the activity and stability of the catalyst, and simultaneously, the carbon precursor can play a role of modifying the active phase structure of the catalyst, being beneficial to improving the selectivity of the cracking catalyst, effectively improving the yield of the target product when the aviation kerosene is used as a target product, and realizing the maximization of the whole benefit of the device.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

The invention provides a startup method of a hydrocracking device, wherein the method comprises the following steps:

The inventor discovers in the study that the leakage of hydrogen sulfide or ammonia gas and excessive cracking reaction in the heating process often occur in the starting process of the existing hydrocracking device, so that the problem of reactor temperature runaway is caused. The ammonia passivation type hydrocracking catalyst is used for startup, the processes of in-device vulcanization and in-device ammonia passivation can be effectively avoided, the use of vulcanizing agents and ammonia gas is reduced, the safety and environmental protection of the startup process of the device are guaranteed, meanwhile, low-nitrogen diesel oil fractions and plant oil with a proper proportion are matched to serve as startup oil, the nitrogen compounds in the low-nitrogen diesel oil are utilized to supplement and passivate the molecular sieve in the catalyst, the stability of the startup heating process is guaranteed, meanwhile, unsaturated hydrocarbons in the startup oil have higher polarity, formed carbon deposition precursors exist around active sites, the activity and stability of the catalyst are improved, and the carbon deposition precursors can also play a role of modifying the active phase structure of the catalyst, so that the selectivity of the hydrocracking catalyst is improved.

In the present invention, the preparation method of the ammonia passivation type sulfidation hydrogenation catalyst is not particularly limited, for example, a method conventionally defined in the art may be selected, for example, sulfidation treatment is performed on the oxidized hydrocracking catalyst in a hydrocracking apparatus by introducing a sulfidation agent, passivation treatment by introducing a passivating agent is not repeated, and other modes may be selected for preparation, as described in detail below.

In a preferred embodiment, in step (1), the method for preparing the ammonia-passivated sulfided hydrocracking catalyst comprises: the oxidation state hydrocracking catalyst is firstly vulcanized outside the hydrocracking device and then is passivated. The advantage of adopting this kind of preferred embodiment is guaranteeing the hydrogenation activity of catalyst and guaranteeing the security of cracking simultaneously, avoids the catalyst to load into the reactor and carries out the vulcanization again and ammonia passivation process, can effectual save time and guarantee convenience and the security of beginning work.

In the present invention, the method of the vulcanization treatment is not particularly limited, and methods conventionally defined in the art are applicable to the present invention. Preferably, in step (1), the vulcanization treatment is wet vulcanization or dry vulcanization.

In a preferred embodiment, the vulcanization process comprises: and vulcanizing the oxidation state hydrocracking catalyst in the presence of a vulcanizing agent and hydrogen to obtain the vulcanized hydrocracking catalyst.

In the present invention, the type of the oxidation state hydrocracking catalyst is not particularly limited, and may be, for example, an oxidation state hydrocracking catalyst conventionally defined in the art, or an oxidation state hydrocracking catalyst (for example, a hydrogenation modifying catalyst) comprising a molecular sieve.

In a preferred embodiment, the oxidation state hydrocracking catalyst comprises a cracking component, a hydrogenation component and a support.

In a preferred embodiment, the cracking component comprises an amorphous acidic component and/or a molecular sieve.

In a preferred embodiment, the amorphous acidic component comprises amorphous silica alumina and/or amorphous silica magnesium.

In a preferred embodiment, the molecular sieve is selected from at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a SAPO molecular sieve, and an MCM-41 mesoporous molecular sieve.

In a preferred embodiment, the hydrogenation component comprises at least one of a group VIII metal and a group VIB metal.

In a preferred embodiment, the group VIII metal is Co and/or Ni and the group VIB metal is Mo and/or W.

In a preferred embodiment, the support comprises a refractory porous material, for example, the refractory porous material is selected from at least one of alumina, silica, titania, magnesia, zirconia, and activated carbon.

In a preferred embodiment, the cracking component is present in an amount of from 10 to 60 wt%, the support is present in an amount of from 30 to 70 wt%, the group VIII metal is present in an amount of from 1 to 15 wt%, and the group VIB metal is present in an amount of from 5 to 30 wt%, based on the weight of the oxidation state hydrocracking catalyst; it is further preferred that the cracking component is present in an amount of from 13 to 50 wt.%, the support is present in an amount of from 35 to 65 wt.%, the group VIII metal is present in an amount of from 3 to 12 wt.%, the group VIB metal is present in an amount of from 8 to 28 wt.%, based on the weight of the oxidized hydrocracking catalyst.

In the present invention, the vulcanization mode is not particularly limited, and vulcanization modes conventionally defined in the art are applicable to the present invention, such as wet vulcanization and dry vulcanization.

In the invention, the selection range of the types of vulcanizing agents in wet vulcanization is wider. Preferably, the vulcanizing agent in the wet vulcanization is selected from at least one of carbon disulfide, dimethyl disulfide, and polysulfide.

In the present invention, the selection range of the kind of the vulcanizing agent in the dry vulcanization is wide. Preferably, the sulfiding agent in the dry sulfiding is selected from at least one of sulfur-containing acid gases, preferably hydrogen sulfide.

In the present invention, the treatment conditions for the dry vulcanization are not particularly limited. Preferably, the conditions of the dry vulcanization treatment include: the heating rate is 5-100 ℃/h, the highest vulcanization temperature is 240-400 ℃, the constant temperature time is 1-15h, the vulcanization pressure is 0.1-10MPa, and the gas agent volume ratio is 50-1000:1, a step of; further preferably, the conditions of the dry vulcanization treatment include: the heating rate is 10-80 ℃/h, the highest vulcanization temperature is 260-380 ℃, the constant temperature time is 2-12h, the vulcanization pressure is 0.3-8MPa, and the gas agent volume ratio is 100-800:1.

In the present invention, the treatment conditions for wet vulcanization are not particularly limited. Preferably, the conditions of the wet vulcanization treatment include: the heating rate is 5-100 ℃/h, the highest vulcanization temperature is 240-400 ℃, the constant temperature time is 1-15h, the vulcanization pressure is 0.1-10MPa, the volume airspeed is 0.3-8 hours ^-1, and the hydrogen-oil volume ratio is 100-1000:1, a step of; further preferably, the conditions of the wet vulcanization treatment include: the heating rate is 10-80 ℃/h, the highest vulcanization temperature is 260-380 ℃, the constant temperature time is 2-12h, the vulcanization pressure is 0.3-8MPa, the volume airspeed is 0.5-6h ^-1, and the hydrogen-oil volume ratio is 150-800:1.

In the present invention, it is preferable to use a dry sulfiding treatment oxidation state hydrocracking catalyst, the specific conditions being as described above.

In the present invention, the manner of passivation treatment is not particularly limited. Preferably, in step (1), the passivation treatment includes: in the presence of an organic solvent, loading an organic nitrogen-containing compound and an organic sulfur-containing compound on a sulfurized hydrogenation catalyst by adopting an impregnation method, and then performing passivation treatment to obtain the ammonia passivation type sulfurized hydrocracking catalyst.

In the present invention, the kind of the organic solvent is not particularly limited. Preferably, the organic solvent is selected from at least one of hydrocarbon oil, hydrocarbon oil oxygen-containing derivative and organic carboxylic ester.

In a preferred embodiment, the hydrocarbon oil and the hydrocarbon oil oxygen-containing derivative are each independently selected from at least one of alcohols, ethers, and light ends hydrocarbon oils, further preferably at least one of ethanol, propanol, butanediol, diethyl ether, cyclohexane, n-heptane, n-decane, methylcyclopentane, naphtha, gasoline, kerosene, diesel oil, white oil, lamp oil, and lubricating oil base oil.

In a preferred embodiment, the organic carboxylic acid ester is a fatty acid glyceride, further preferably at least one of corn oil, peanut oil, soybean oil, olive oil, and cottonseed oil.

In the present invention, the range of selection of the number of carbon atoms of the organic solvent is wide. Preferably, the organic solvent has a carbon number of 2 to 35, preferably 5 to 30, more preferably 10 to 20.

The organic solvent has the advantages of better dissolving most of nitrogen-containing compounds and sulfur-containing compounds, simultaneously only comprising carbon, hydrogen and oxygen elements, and not containing other impurity elements, and being better mutually dissolved with starting oil in the subsequent starting operation.

In the present invention, the type of the organic nitrogen-containing compound is not particularly limited, and may be selected by those skilled in the art according to actual requirements. Preferably, the organic nitrogen-containing compound is at least one selected from the group consisting of alkylamine compounds, arylamine compounds, aniline compounds, methylaniline compounds, amide compounds, alcohol amine compounds and polyamine compounds, more preferably alkylamine compounds and/or alcohol amine compounds, still more preferably alkylamine compounds and alcohol amine compounds, and for example, may be at least one selected from the group consisting of ethylenediamine, propylamine, butylamine, pentylamine, hexylamine, triethylamine, t-butylamine, N-dihydroxyethylaniline, acetanilide, ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N- (2-hydroxyethyl) ethylenediamine, N-methyldiethanolamine, N-diisopropylethanolamine, 1, 2-cyclohexanediamine, 1, 3-propylenediamine, triethylenediamine, N-dimethyldipropylene triamine, triethylenetetramine and hexamethylenetetramine.

In the present invention, the selection range of the number of carbon atoms of the organic nitrogen-containing compound is wide. Preferably, the organic nitrogen-containing compound has a carbon number of 1 to 20, preferably 2 to 15.

The organic nitrogen-containing compound has the advantages that the nitrogen-containing compound has the characteristic of weak alkalinity, can well form good acid-base adsorption with the acid position on the molecular sieve, covers the acid position, and ensures that the proper carbon number can be well dissolved in the solvent.

In the present invention, the type of the organic sulfur-containing compound is not particularly limited. Preferably, the organic sulfur-containing compound is at least one selected from the group consisting of thiol compounds, thiophenol compounds, thioether compounds, thiourea compounds, sulfone compounds, sulfoxide compounds, sulfonic acid compounds, sulfinic acid compounds and disulfides, more preferably thioether compounds and/or disulfides, still more preferably thioether compounds and disulfides, and for example, may be at least one selected from the group consisting of carbon disulfide, dimethyl disulfide, dibutyl-sulfide, dibutyl-disulfide, dibutyl-trisulfide and dibutyl-tetrasulfide, and derivatives thereof.

In the present invention, the carbon number of the organic sulfur-containing compound is selected in a wide range. Preferably, the organic sulfur-containing compound has a carbon number of 1 to 15, preferably 1 to 10.

The organic sulfur-containing compound has the advantages that the sulfur content is relatively high, the catalyst can be decomposed to form hydrogen sulfide by reacting with hydrogen at a certain temperature in the starting process, the catalyst is subjected to complementary vulcanization, and meanwhile, the catalyst and the solvent can be better intersoluble, so that the sulfur-containing organic solvent is formed and impregnated into the catalyst.

In a preferred embodiment, the organic nitrogen-containing compound, the organic sulfur-containing compound and the organic solvent are used in amounts such that the ammonia-passivated sulfided hydrocracking catalyst comprises from 0.1 to 5% by weight of nitrogen as elemental and from 0.1 to 3% by weight of sulfur as elemental; further preferably, the nitrogen content in terms of elements is 0.5to 3% by weight of the hydrocracking catalyst in the sulfided state before deactivation, and the sulfur content in terms of elements is 0.3 to 2% by weight of the hydrocracking catalyst in the sulfided state before deactivation.

In the present invention, a conventionally defined impregnation method may be selected, and for example, saturated impregnation, unsaturated impregnation or supersaturated impregnation may be used. Preferably, the supporting may be performed in at least one manner, for example, the sulfided hydrogenation catalyst may be immersed in a solution containing the organic nitrogen-containing compound and the organic sulfur-containing compound in the presence of an organic solvent; the solution containing the organic nitrogen-containing compound and the organic sulfur-containing compound may also be sprayed onto the sulfided hydrogenation catalyst in the presence of an organic solvent.

In the present invention, the conditions for supporting the organic nitrogen-containing compound and the organic sulfur-containing compound by the impregnation method are not particularly limited. Preferably, the loading temperature is 10-100 ℃, preferably 20-90 ℃.

In the invention, the condition selection range of the passivation treatment is wider. Preferably, the passivation treatment conditions include: the temperature is 10-120 ℃, the pressure is 0.01-0.5MPa, and the time is 0.5-10h; further preferably, the passivation treatment conditions include: the temperature is 10-100 ℃, the pressure is 0.03-0.3MPa, and the time is 1-8h; still further preferably, the conditions of the passivation treatment include: the temperature is 20-80 ℃, the pressure is 0.05-0.15MPa, and the time is 2-6h.

In the present invention, the pressure is absolute pressure.

In a preferred embodiment, the passivation treatment is performed under a passivation atmosphere.

In the present invention, the passivation atmosphere is selected in a wide range, and may be a passivation atmosphere conventionally defined in the art. Preferably, the passivation atmosphere is selected from at least one of inert gas, aerobic atmosphere and air.

In a preferred embodiment, the inert atmosphere is selected from at least one of nitrogen, helium and argon.

In a preferred embodiment, the passivation treatment is carried out in a stationary treatment apparatus.

In a preferred embodiment, the passivation treatment is performed in a non-flowing atmosphere, a naturally moving atmosphere, or a forced flowing atmosphere.

In the invention, the temperature of the reaction bed layer is raised by introducing hydrogen into the reaction bed layer as a heating medium. Preferably, in step (2), the temperature of the hydrogen is 150-230 ℃, further preferably 150-200 ℃.

In the present invention, the rate of temperature rise of the reaction bed is not particularly limited as long as the desired temperature is reached. Preferably, in the step (2), hydrogen is introduced to raise the temperature of the reaction bed at a heating rate of 5-20 ℃/h, preferably 5-15 ℃/h.

In a preferred embodiment, in step (2), hydrogen is introduced to raise the temperature of the reaction bed to 110-140 ℃. The advantage of adopting this preferred embodiment is that part of the liquid water contained in the catalyst, the reactor, the pipeline and the like is removed, so that the catalyst structure is prevented from being damaged by steam formed after the subsequent temperature rise.

In the invention, the diesel fraction is introduced into the step (2) as starting oil, and the starting treatment is carried out to meet the starting requirement. Preferably, in step (2), the diesel fraction is selected from at least one of straight run diesel, catalytically cracked diesel, coker diesel and hydrocracked diesel, preferably straight run diesel and/or hydrocracked diesel.

In a preferred embodiment, the diesel fraction has a distillation range of 180-380 ℃, preferably 180-360 ℃.

In a preferred embodiment, the nitrogen content of the diesel fraction is in the range of 0 to 900ppm, preferably 0 to 500ppm, more preferably 10 to 300ppm.

In the invention, the diesel oil fraction with the types and parameters is selected as the starting oil, so that the catalyst has the advantages of dissolving the solvent oil on the catalyst and providing a certain amount of nitride to supplement and deactivate the acid sites of the molecular sieve on the catalyst.

In the present invention, the kind of the vegetable oil is not particularly limited, and may be a vegetable oil conventionally defined in the art. Preferably, the vegetable oil is selected from at least one of corn oil, soybean oil, peanut oil, canola oil, coconut oil, sunflower oil, olive oil and cottonseed oil, preferably at least one of corn oil, soybean oil, peanut oil, canola oil, coconut oil, sunflower oil and cottonseed oil.

In a preferred embodiment, the vegetable oil has a distillation range of 200-540 ℃ and a bromine number of 10-25gBr/100mL; preferably, the vegetable oil has a distillation range of 210-530 ℃ and a bromine valence of 12-20gBr/100mL. The advantage of adopting this kind of preferred embodiment is that can effectively guarantee the promotion of catalyst activity and stability under the effect of vegetable oil follow-up, utilizes the modification effect of carbon deposition precursor, helps hydrocracking catalyst selectivity's improvement.

In the present invention, the amounts of diesel fraction and vegetable oil used are not particularly limited. Preferably, the diesel fraction is used in an amount of 100 to 2000 parts by weight and the vegetable oil is used in an amount of 0 to 300 parts by weight, compared to 100 parts by weight of the hydrocracking catalyst; it is further preferred that the diesel fraction is used in an amount of 200 to 1500 parts by weight and the vegetable oil is used in an amount of 10 to 250 parts by weight, compared to 100 parts by weight of the hydrocracking catalyst.

According to the invention, the low-nitrogen diesel fraction and/or the vegetable oil is selected as the starting oil, so that the method has the advantages of supplementing passivation effect and improving the activity and stability of the catalyst, and simultaneously the selectivity of the catalyst and the yield of a target product can be effectively improved by using the starting oil. In the prior art, straight-run diesel oil is usually selected as starting oil, and the defects that passivation cannot be supplemented, temperature runaway is easy to cause, and the active phase structure of the catalyst cannot be modified are overcome.

In the present invention, the conditions of the closed cycle are not particularly limited. Preferably, in step (2), the closed cycle conditions include: the pressure is 8-17MPa, and the hydrogen oil volume ratio is 300:1-1000:1, the volume airspeed is 0.5-3h ^-1; further preferably, the pressure is 8-15MPa, and the hydrogen-oil volume ratio is 500:1-1000:1, the volume space velocity is 0.5-2h ^-1. The advantage of adopting this kind of preferred embodiment is that the organic solvent that carries on the passivation type sulfuration catalyst of ammonia dissolves or decomposes better, is favorable to the nitride in the oil of starting to combine with the acidic site on the molecular sieve simultaneously, plays the effect of supplementary passivation to guarantee that unsaturated hydrocarbon forms the condensation of certain degree around the active site.

In a preferred embodiment, in step (3), the temperature of the reaction bed in step (2) is continuously increased to 310-350 ℃. An advantage of using such a preferred embodiment is that it reduces the activity affected by excessive cracking of the startup oil at high temperature and excessive condensation of unsaturated hydrocarbons.

In the present invention, the rate of temperature increase in step (3) is not particularly limited. Preferably, in the step (3), the temperature rise rate of the temperature rise of the reaction bed layer is 10-35 ℃/h, preferably 10-30 ℃/h.

In the present invention, the type of the raw oil is not particularly limited. Preferably, in step (3), the raw oil is at least one selected from straight-run wax oil, straight-run diesel oil and catalytic diesel oil.

In a preferred embodiment, the feedstock has a density of 0.85 to 1.0g.cm ^-3, a sulfur content of 0.5 to 2wt%, a nitrogen content of 0.05 to 0.6wt% and a distillation range of 350 to 500 ℃.

In a preferred embodiment, in step (3), the hydrocracking reaction conditions include: the reaction temperature is 300-380 ℃, the pressure is 8-17MPa, the hydrogen-oil volume ratio is 300-1000, and the volume airspeed is 0.5-3h ^-1.

The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

The properties of the starting oil and the raw oil used in the following examples and comparative examples are shown in Table 1.

TABLE 1

For illustrating the characteristics of the present invention, the commercial oxidation state hydrocracking catalyst with 3 wt% of Ni oxide, 27 wt% of W oxide, 35 wt% of Y-type molecular sieve and the balance of alumina produced in the same batch of industrial production is selected in the examples and comparative examples, and is vulcanized by using a combination gas of hydrogen sulfide and hydrogen gas by dry vulcanization, and the vulcanization treatment is performed outside the hydrocracking apparatus under the following conditions: the volume fraction of H ₂ S is 3%, the volume fraction of H ₂ is 97%, the heating rate is 20 ℃/H, the vulcanization temperature is 340 ℃, the constant temperature time is 8H, the vulcanization pressure is 4MPa, and the gas-agent volume ratio is 400:1, obtaining the vulcanized hydrocracking catalyst. In the examples and the comparative examples, wax oil is used as a raw material, and aviation kerosene main products and other series of low-carbon products are obtained through hydrocracking.

Example 1

Filling a hydrocracking device with a hydrocracking catalyst, starting a circulating hydrogen compressor after the hydrocracking device is airtight qualified, heating the bed layer of the hydrocracking device through hydrogen, wherein the heating rate is 15 ℃/h, controlling the temperature of the bed layer at 140 ℃, starting to introduce a starting diesel A into the hydrocracking device for wetting and flushing the bed layer, switching the starting diesel A and the vegetable oil C for closed circulation after the bed layer is fully wetted and flushed, wherein the weight ratio of the diesel A to the catalyst is 15, the weight ratio of the vegetable oil C to the catalyst is 2.5, heating the bed layer at the speed of 30 ℃/h, when the temperature reaches 350 ℃, switching the raw oil, gradually increasing the reaction temperature to the qualified product through a heating furnace, starting to formally react at the temperature at the moment, wherein the operating conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1, and performing simulated distillation on the product under the specific test conditions that: analyzing a sample by adopting a measuring method of multi-dimensional gas chromatography SH/T0558-2016 petroleum fraction boiling range distribution, determining the proportion of each fraction section according to different distillation ranges, carrying out unloading characterization on a catalyst after the reaction is completed, carrying out HRTEM characterization analysis on an active phase structure of the catalyst, wherein the active phase is a microstructure with catalytic activity in the catalyst, and particularly has a Ni-W-S form, and the whole of the active phase is a lamellar crystal structure, wherein the projection of the lamellar structure can be observed by a high-resolution transmission electron microscope to be a streak phase with different lengths, and generally, the shorter the streak phase is, the higher the catalytic activity is, and the specific test conditions are as follows: the sample is characterized by using a Tecnai G2F 20S-TWIN high-resolution transmission electron microscope (HRTEM) produced by FEI company, the accelerating voltage is 200kV, the size and stacking condition of WS ₂ platelets in the sample are observed, when the sample is prepared, the ground sample is subjected to ultrasonic dispersion treatment in cyclohexane solution, and a small amount of upper suspension liquid drops are collected on a copper mesh of a carbon coating.

The method comprises the steps of adding a hydrocracking catalyst into diesel oil, uniformly stirring at 90 ℃ to obtain a nitrogen-sulfur solution, introducing the nitrogen-sulfur solution into the hydrocracking catalyst in a saturated impregnation mode, loading 3 weight percent of nitrogen content and 2 weight percent of sulfur content, wherein nitrogen is from tri-n-butylamine, and sulfur is from dimethyl disulfide; then passivating for 8 hours at 100 ℃ under 0.3MPa in flowing nitrogen atmosphere to prepare the ammonia passivation type sulfur hydrocracking catalyst.

Example 2

After the hydrocracking device is filled with a hydrocracking catalyst, a circulating hydrogen compressor is started after the hydrocracking device is qualified in airtight, the temperature of the bed layer of the hydrocracking device is raised by hydrogen, the temperature raising rate is 10 ℃/h, so that the temperature of the bed layer is controlled to be 125 ℃, the wetting and flushing of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil C are switched to perform closed circulation, wherein the weight ratio of the diesel oil A to the catalyst is 10, the weight ratio of the vegetable oil C to the catalyst is 1, the bed layer is raised at the speed of 15 ℃/h, the temperature reaches 335 ℃, the raw oil is switched, the reaction temperature is gradually raised to be qualified by a heating furnace, the temperature is 361 ℃ at the moment, the formal reaction is started, the operating conditions of the temperature raising and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

The method comprises the steps of adding a hydrocracking catalyst into diesel oil, stirring uniformly at 50 ℃ to obtain a nitrogen-sulfur solution, introducing the nitrogen-sulfur solution into the hydrocracking catalyst in a saturated impregnation mode, loading 2 weight percent of nitrogen content and 1 weight percent of sulfur content, wherein nitrogen is from tri-n-butylamine, and sulfur is from dimethyl disulfide; then passivating for 4 hours at 40 ℃ under 0.1MPa in flowing nitrogen atmosphere to prepare the ammonia passivation type sulfuration hydrocracking catalyst.

Example 3

After the hydrocracking device is filled with a hydrocracking catalyst, a circulating hydrogen compressor is started after the hydrocracking device is qualified in airtight, the temperature of the bed layer of the hydrocracking device is raised through hydrogen, the temperature raising rate is 5 ℃/h, so that the temperature of the bed layer is controlled at 110 ℃, the wetting and flushing of the bed layer of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil C are switched to perform closed circulation, wherein the weight ratio of the diesel oil A to the catalyst is 2, the weight ratio of the vegetable oil C to the catalyst is 0.1, the bed layer is raised at the speed of 10 ℃/h, the temperature reaches 310 ℃, the raw oil is switched, the reaction temperature is gradually raised to be qualified through a heating furnace, the temperature is 362 ℃ at the moment, the formal reaction is started, the operating conditions of the temperature raising and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

The method comprises the steps of adding a hydrocracking catalyst into diesel oil, stirring uniformly at 20 ℃ to obtain a nitrogen-sulfur solution, introducing the nitrogen-sulfur solution into the hydrocracking catalyst in a sulfur state according to a saturated impregnation mode, loading 0.5 weight percent of nitrogen content and 0.3 weight percent of sulfur content, wherein nitrogen is from tri-n-butylamine, and sulfur is from dimethyl disulfide; then passivating for 1 hour under the flowing nitrogen atmosphere at 10 ℃ and 0.03MPa to prepare the ammonia passivation type sulfuration hydrocracking catalyst.

Example 4

Filling the hydrocracking device with the catalyst in the embodiment 2, starting a circulating hydrogen compressor after the device is qualified in airtight, heating the bed of the hydrocracking device through hydrogen at a heating rate of 10 ℃/h, controlling the temperature of the bed at 125 ℃, starting to introduce the wetting and flushing bed of the starting diesel oil B into the hydrocracking device, switching the starting diesel oil B and the vegetable oil C to perform closed circulation after the bed is fully wetted and flushed, wherein the weight ratio of the diesel oil B to the catalyst is 10, the weight ratio of the vegetable oil C to the catalyst is 1, heating the bed at a speed of 15 ℃/h, switching the raw oil when the temperature reaches 335 ℃, gradually increasing the reaction temperature to be qualified through a heating furnace, starting to perform the reaction formally at the temperature of 365 ℃, wherein the operating conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Example 5

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the bed layer of the hydrocracking device is heated by hydrogen, the heating rate is 10 ℃/h, the temperature of the bed layer is controlled at 125 ℃, the wetting and flushing of the bed layer of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil C are switched to carry out closed cycle, wherein the weight ratio of the diesel oil A to the catalyst is 1.5, the weight ratio of the vegetable oil C to the catalyst is 0.08, the bed layer is heated at the rate of 15 ℃/h, when the temperature reaches 335 ℃, the raw oil is switched, the reaction temperature is gradually increased to be qualified by a heating furnace, the temperature is 366 ℃, the formal reaction is started, the operating conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Example 6

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the bed layer of the hydrocracking device is heated by hydrogen, the heating rate is 20 ℃/h, the temperature of the bed layer is controlled to be 105 ℃, the wetting and flushing of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil C are switched to carry out closed cycle, wherein the weight ratio of the diesel oil A to the catalyst is 18, the weight ratio of the vegetable oil C to the catalyst is 0.05, the bed layer is heated at the speed of 35 ℃/h, when the temperature reaches 300 ℃, the raw oil is switched, the reaction temperature is gradually increased to be qualified by a heating furnace, the temperature is 365 ℃, the reaction is started to be formally carried out, the operating conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Example 7

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the bed layer of the hydrocracking device is heated by hydrogen, the heating rate is 12 ℃/h, so that the temperature of the bed layer is controlled at 130 ℃, the wetting and flushing of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil D are switched to carry out closed circulation, wherein the weight ratio of the diesel oil A to the catalyst is 10, the weight ratio of the vegetable oil D to the catalyst is 1, the bed layer is heated at the speed of 20 ℃/h, the temperature reaches 340 ℃, the raw oil is switched, the reaction temperature is gradually increased to be qualified by a product through a heating furnace, the temperature is 366 ℃, the reaction starts to be formally carried out, the operation conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen is 800:1, and the volume airspeed is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Example 8

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the temperature of the bed layer of the hydrocracking device is raised through hydrogen, the temperature raising rate is 15 ℃/h, so that the temperature of the bed layer is controlled to be 125 ℃, the wetting and flushing of the diesel A bed layer is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, closed circulation is carried out, the temperature of the bed layer is raised according to the rate of 20 ℃/h, when the temperature reaches 330 ℃, the raw oil is switched, and meanwhile, the reaction temperature is gradually raised to be qualified through a heating furnace, at the moment, the temperature is 369 ℃, the formal reaction is started, the operating conditions of the temperature raising and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen to the oil is 800:1, and the volume airspeed is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Comparative example 1

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the temperature of the bed layer of the hydrocracking device is raised through hydrogen, the temperature raising rate is 10 ℃/h, so that the temperature of the bed layer is controlled at 130 ℃, raw oil is introduced into the hydrocracking device to moisten and rinse the bed layer, closed circulation is carried out after the bed layer is fully moistened and rinsed, the temperature of the bed layer is raised according to the rate of 20 ℃/h, when the temperature reaches 320 ℃, the reaction temperature is gradually raised to be qualified by a heating furnace, the temperature is 375 ℃, the formal reaction is started, the operating conditions of the temperature raising and the reaction process are that the pressure is 13MPa, the hydrogen oil volume ratio is 800:1, and the volume airspeed is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Comparative example 2

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the temperature of the bed layer of the hydrocracking device is raised through hydrogen, the temperature raising rate is 15 ℃/h, so that the temperature of the bed layer is controlled to be 140 ℃, the wetting and flushing of the vegetable oil C into the hydrocracking device are started, after the bed layer is fully wetted and flushed, closed circulation is carried out, the temperature of the bed layer is raised according to the speed of 15 ℃/h, when the temperature reaches 330 ℃, the raw oil is switched, the reaction temperature is gradually raised to be qualified through a heating furnace, at the moment, the temperature is 372 ℃, the formal reaction is started, the operating conditions of the temperature raising and the reaction process are 13MPa, the hydrogen-oil volume ratio is 800:1, and the volume airspeed is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Comparative example 3

The catalyst in the embodiment 2 is added into the hydrocracking device, after the device is qualified in airtight, a circulating hydrogen compressor is started, the bed layer of the hydrocracking device is heated by hydrogen, the heating rate is 35 ℃/h, the temperature of the bed layer is controlled to be 150 ℃, the wetting and flushing of the starting diesel oil A is started to be introduced into the hydrocracking device, after the bed layer is fully wetted and flushed, the starting diesel oil A and the vegetable oil C are switched to carry out closed cycle, wherein the weight ratio of the diesel oil A to the catalyst is 0.8, the weight ratio of the vegetable oil C to the catalyst is 4, the bed layer is heated at the speed of 5 ℃/h, the temperature reaches 280 ℃, then the raw oil is switched, the reaction temperature is gradually increased to be qualified by a heating furnace, the temperature is 370 ℃, the reaction is started to be formally carried out, the operating conditions of the heating and the reaction process are that the pressure is 13MPa, the volume ratio of the hydrogen oil is 800:1, and the volume space velocity is 1h ^-1. The product was distilled simulated as in example 1, the ratio of each fraction was determined, the catalyst was subjected to a catalyst removal characterization after the reaction was completed, and the active phase structure of the catalyst was subjected to HRTEM characterization analysis.

Comparing the effects of the examples with those of the comparative examples in tables 2-4, wherein the reaction temperature of the device is examined under the condition that the product indexes are qualified by analyzing that each fraction section in the product reaches corresponding product indexes (the fraction section is 140-240 ℃ and is aviation kerosene, the thiol sulfur content is less than 0.002%, the smoke point is not less than 25.0mm, the freezing point is not higher than-47 ℃), and the activity of the catalyst is considered to be higher as the reaction temperature is lower, specifically shown in table 2; the higher the aviation kerosene yield, the better the selectivity of the representative catalyst, see in particular table 3; the shorter the length of the catalyst active phase, the higher the catalyst activity potential, see in particular table 4.

Wherein yield (%) of aviation kerosene = weight of aviation kerosene/total weight of product x 100%.

Wherein, the stripe length of the active phase of the catalyst is measured by a high resolution transmission electron microscope, a sample of the stripe length is required to be counted, 20 pictures are taken, the stripe length of the stripe phase on the pictures is counted, and the average length of WS ₂ platelets is countedCalculated according to the formula.

Average length of platelets(Unit: nm):

Wherein: l _i is the length of the ith WS ₂ platelet stripe phase; n is the total number of platelets in the statistical region.

TABLE 2

TABLE 3 Table 3

TABLE 4 Table 4

The embodiment and the comparative example show that the method has the greatest advantages that the method is optimized and improved aiming at some defects existing in the existing starting method, avoids the safety and environmental protection risks caused by vulcanizing agents, avoids the overtemperature risks caused by in-device activation, reduces the use and emission of toxic substances such as ammonia gas and the like, reduces the waste of passivating agents and the like, and simultaneously forms a certain carbon deposition precursor on the surface of the catalyst due to the special property of the starting oil by matching the starting oil with the vegetable oil, slows down the growth of the active phase size of the catalyst, effectively improves the activity of the catalyst reaction and the selectivity of target products, realizes qualified products at lower temperature, simultaneously obtains higher aviation kerosene yield and improves the added value of the products.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims

1. A method of operating a hydrocracking apparatus, the method comprising:

(3) Continuously heating the temperature of the reaction bed layer in the step (2) to 300-350 ℃, then switching raw oil, and continuously heating to the hydrocracking reaction temperature;

2. The method of claim 1, wherein,

In the step (1), the preparation method of the ammonia passivation type sulfided hydrocracking catalyst comprises the following steps: the oxidation state hydrocracking catalyst is firstly vulcanized outside the hydrocracking device and then is passivated.

3. The method of claim 2, wherein in step (1), the vulcanization treatment is wet vulcanization or dry vulcanization;

Preferably, the vulcanization treatment includes: vulcanizing the oxidation state hydrocracking catalyst in the presence of a vulcanizing agent and hydrogen to obtain a vulcanization state hydrocracking catalyst;

preferably, the oxidation state hydrocracking catalyst comprises a cracking component, a hydrogenation component and a support;

Preferably, the cracking component comprises an amorphous acidic component and/or a molecular sieve, the amorphous acidic component comprises amorphous silica alumina and/or amorphous silica magnesia, and the molecular sieve is selected from at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a SAPO molecular sieve and an MCM-41 mesoporous molecular sieve;

preferably, the hydrogenation component comprises at least one of a group VIII metal and a group VIB metal;

Preferably, the support comprises a refractory porous material selected from at least one of alumina, silica, titania, magnesia, zirconia, and activated carbon;

Preferably, the cracking component is present in an amount of from 10 to 60 wt%, the support is present in an amount of from 30 to 70 wt%, the group VIII metal is present in an amount of from 1 to 15 wt%, and the group VIB metal is present in an amount of from 5 to 30 wt%, based on the weight of the oxidation state hydrocracking catalyst; further preferably, the cracking component is present in an amount of from 13 to 50 wt%, the support is present in an amount of from 35 to 65 wt%, the group VIII metal is present in an amount of from 3 to 12 wt%, and the group VIB metal is present in an amount of from 8 to 28 wt%, based on the weight of the oxidized hydrocracking catalyst;

Preferably, the vulcanizing agent in the wet vulcanization is selected from at least one of carbon disulfide, dimethyl disulfide and polysulfide;

preferably, the vulcanizing agent in the dry vulcanization is hydrogen sulfide and/or hydrogen;

preferably, the conditions of the dry vulcanization treatment include: the heating rate is 5-100 ℃/h, the highest vulcanization temperature is 240-400 ℃, the constant temperature time is 1-15h, the vulcanization pressure is 0.1-10MPa, and the gas agent volume ratio is 50-1000:1, a step of; further preferably, the conditions of the dry vulcanization treatment include: the heating rate is 10-80 ℃/h, the highest vulcanization temperature is 260-380 ℃, the constant temperature time is 2-12h, the vulcanization pressure is 0.3-8MPa, and the gas agent volume ratio is 100-800:1, a step of;

Preferably, the conditions of the wet vulcanization treatment include: the heating rate is 5-100 ℃/h, the highest vulcanization temperature is 240-400 ℃, the constant temperature time is 1-15h, the vulcanization pressure is 0.1-10MPa, the volume airspeed is 0.3-8 hours ^-1, and the hydrogen-oil volume ratio is 100-1000:1, a step of; further preferably, the conditions of the wet vulcanization treatment include: the heating rate is 10-80 ℃/h, the highest vulcanization temperature is 260-380 ℃, the constant temperature time is 2-12h, the vulcanization pressure is 0.3-8MPa, the volume airspeed is 0.5-6 hours ^-1, and the hydrogen-oil volume ratio is 150-800:1.

4. The method of claim 2, wherein in step (1), the passivation process comprises: under the condition of the existence of an organic solvent, loading an organic nitrogen-containing compound and an organic sulfur-containing compound on a sulfurized hydrogenation catalyst by adopting an impregnation method, and then performing passivation treatment to obtain an ammonia passivation type sulfurized hydrocracking catalyst;

preferably, the organic solvent is selected from at least one of hydrocarbon oil, hydrocarbon oil oxygen-containing derivative and organic carboxylic ester;

preferably, the hydrocarbon oil and the hydrocarbon oil oxygen-containing derivative are each independently selected from at least one of alcohols, ethers, and light-fraction hydrocarbon oils;

Preferably, the organic carboxylic acid ester is a fatty acid glyceride;

preferably, the organic solvent has a carbon number of 2 to 35, preferably 5 to 30, further preferably 10 to 20;

Preferably, the organic nitrogen-containing compound is at least one selected from alkylamine compounds, arylamine compounds, aniline compounds, methylaniline compounds, amide compounds, alcohol amine compounds and polyamine compounds, and more preferably alkylamine compounds and/or alcohol amine compounds;

Preferably, the organic nitrogen-containing compound has a carbon number of 1 to 20, preferably 2 to 15;

preferably, the organic sulfur-containing compound is selected from at least one of a thiol compound, a thiophenol compound, a thioether compound, a thiourea compound, a sulfone compound, a sulfoxide compound, a sulfonic acid compound, a sulfinic acid compound and a disulfide, and more preferably, a thioether compound and/or a disulfide;

preferably, the organic sulfur-containing compound has a carbon number of 1 to 15, preferably 1 to 10;

Preferably, the organic nitrogen-containing compound, the organic sulfur-containing compound and the organic solvent are used in an amount such that the ammonia passivation type hydrocracking catalyst has a nitrogen content of 0.1 to 5% by weight of the hydrocracking catalyst in a vulcanized state before passivation, and a sulfur content of 0.1 to 3% by weight of the hydrocracking catalyst in a vulcanized state before passivation;

Further preferably, the content of nitrogen in terms of element is 0.5 to 3% by weight of the sulfided hydrocracking catalyst before deactivation, and the content of sulfur in terms of element is 0.3 to 2% by weight of the sulfided hydrocracking catalyst before deactivation;

preferably, the loading temperature is 10-100 ℃, preferably 20-90 ℃;

Preferably, the passivation treatment conditions include: the temperature is 10-120 ℃, the pressure is 0.01-0.5MPa, and the time is 0.5-10h;

further preferably, the passivation treatment conditions include: the temperature is 10-100 ℃, the pressure is 0.03-0.3MPa, and the time is 1-8h;

preferably, the passivation treatment is performed under a passivation atmosphere;

preferably, the passivation atmosphere is selected from at least one of inert gas, aerobic atmosphere and air;

Preferably, the inert atmosphere is selected from at least one of nitrogen, helium and argon;

Preferably, the passivation treatment is performed in a stationary treatment apparatus;

Preferably, the passivation treatment is performed in a non-flowing atmosphere, a naturally moving atmosphere, or a forced flowing atmosphere.

5. The process according to claim 1 or 2, wherein in step (2) the temperature of the hydrogen is 150-230 ℃, further preferably 150-200 ℃;

Preferably, in the step (2), hydrogen is introduced to raise the temperature of the reaction bed layer at a heating rate of 5-20 ℃/h, preferably 5-15 ℃/h;

preferably, in the step (2), hydrogen is introduced to raise the temperature of the reaction bed to 110-140 ℃.

6. The process according to claim 1 or 2, wherein in step (2) the diesel fraction is selected from at least one of straight run diesel, catalytically cracked diesel, coker diesel and hydrocracked diesel, preferably straight run diesel and/or hydrocracked diesel;

Preferably, the diesel fraction has a distillation range of 180-380 ℃, preferably 180-360 ℃;

7. The method according to claim 1 or 2, wherein in step (2) the vegetable oil is selected from at least one of corn oil, soybean oil, peanut oil, canola oil, coconut oil, sunflower oil, olive oil and cottonseed oil, preferably at least one of corn oil, soybean oil, peanut oil, canola oil, coconut oil, sunflower oil and cottonseed oil;

preferably, the vegetable oil has a distillation range of 200-550 ℃ and a bromine valence of 10-25gBr/100mL; further preferably, the vegetable oil has a distillation range of 210-530 ℃ and a bromine number of 12-20gBr/100mL;

preferably, the diesel fraction is used in an amount of 100 to 2000 parts by weight and the vegetable oil is used in an amount of 0 to 300 parts by weight, compared to 100 parts by weight of the hydrocracking catalyst;

It is further preferred that the diesel fraction is used in an amount of 200 to 1500 parts by weight and the vegetable oil is used in an amount of 10 to 250 parts by weight, compared to 100 parts by weight of the hydrocracking catalyst.

8. The method of claim 1 or 2, wherein in step (2), the closed cycle conditions comprise: the pressure is 8-17MPa, and the hydrogen oil volume ratio is 300:1-1000:1, the volume airspeed is 0.5-3h ^-1;

Preferably, the pressure is 8-15MPa, and the hydrogen-oil volume ratio is 500:1-1000:1, the volume space velocity is 0.5-2h ^-1.

9. The method according to claim 1 or 2, wherein in step (3), the reaction bed temperature of step (2) is continuously raised to 310-350 ℃;

Preferably, in the step (3), the temperature rise rate of the temperature rise of the reaction bed layer is 10-35 ℃/h, preferably 10-30 ℃/h.

10. The method according to claim 1 or 2, wherein in step (3), the feedstock oil is selected from at least one of straight run wax oil, straight run diesel oil and catalytic diesel oil;

Preferably, the density of the raw oil is 0.85-1g.cm ^-3, the sulfur content is 0.5-2wt%, the nitrogen content is 0.05-0.6wt%, and the distillation range is 350-500 ℃.